Methoxy vinylnaphthalenes and polymers thereof



United States Patent METHOXY VINYLNAPHTHALENES AND POLYMERS THEREOF JackL. R. Williams, Rochester, N. Y., assignor to Eastman Kodak Company,Rochester, N. Y., a corporation of New .Iersey No Drawing. ApplicationJune 15, 1953, Serial No. 361,815

11 Claims. (Cl. 260-47) This invention relates to vinylnaphthalenecompounds and particularly to alkoxy vinylnaphthalene and polymersthereof.

Certain alkoxyvinylnaphthalenes have previously been described in theliterature but polymers of alkoxyvinylnaphthalenes have not previouslybeen prepared. Van Allan, J. Org. Chem. pp. 999-1001, 1951, prepared 4-methoxy-l-vinylnaphthalene I and Cohen et a1. preparedG-methoxy-l-vinylnaphthalene II. The workers reported that compounds Iand II form the respective Diels-Alder maleic anhydride adducts.

from I from II R in which R is either a hydrogen atom or an alkoxy groupsuch as methoxy, ethoxy and the like, preferably containing from 1 to 4acrbon atoms.

The following representative alkoxyvinylnaphthalenes are readilyprepared by this process:

I 4-methoxy-l-vinylnaphthalene II 6-methoxy-l-vinylnaphthalene III6-methoxy-Z-vinylnaphthalene IV l-methoxy-2-vinylnaphthalene CH=CHz HAOCompounds III and IV have not previously been prepared and areparticularly distinguished from compounds I and II by the fact that theydo not form a Diels-Alder maleic anhydride adduct. Compound IV isparticularly notable since its resinous polymers can be demethylated soas to yield a 2-vinyl-l-naphthol polymer of use in color photography asa dye coupler for silver halide emulsion layers developed with primaryaromatic amino silver halide developing agents. Polymers of compounds I,II and III, upon demethylation, do not couple with primary aromaticamino silver halide developing agents to form dye images in the emulsionlayers.

The resinous polymers (both homopolymers and copolymers) of thealkoxyvinylnaphthalene compound such as polymers of compounds I-IV, forma valuable part of my invention. The polymers are obtained byapplication of well-known methods of polymerization preferably including the use of heat, ultraviolet light and polymerization catalyst suchas benzoyl peroxide, hydrogen peroxide, or potassium persulfate.Copolymers of the alkoxyvinylnaphthalenes are prepared in a well-knownmanner by polymerization of a mixture of about 5 to percent of thealkoxyvinylnaphthalene compound, preferably in the presence ofcatalysts, with about 95 to 5 percent of one or more compoundscontaining a polymerizable CH=C'- group such as maleic anhydride, vinylhalides, acrylic and alkacrylic acids, amides and esters, furnarates,maleates, a-acylamido acrylic acids and esters, alkylalkenyl ketones,ot-acyloxyalkenonitriles, alkenylnitriles, and hydrocarbons containingconjugated olefinic unsaturation such as the styrenes. Specificcompounds useful in making copolymers of the alkoxyvinylnaphthalenecompounds are vinyl chloride, vinylmethyl ketone, methyl fumarate,acrylonitrile, styrene, 0-, m-, p-methylstyrenes, methylmethacrylate,methylacrylate, acrylamide, and a-methacrylic acid. The polymers of thecompounds of the invention are resinous materials distinct in physicalproperties from crystalline materials such as dimers of thealkoxyvinylnaphthalenes.

As will be apparent from the following description of my process forpreparing the alkoxyvinylnaphthalene compounds, the selectednaphthylmethylcarbinol acetate is passed through a zone such as avitreous tube heated to a temperature of about 500 C. However, thepyrolysis can be carried out within a range of temperature of about 250to 600 C. It is preferable to introduce the naphthylmethylcarbinolacetate into the pyrolytic chamber in conjunction with an inert solventsuch as benzene although the compound can less readily be introduced infinely ground crystalline form. Following pyrolysis, thevinylnaphthalene compound is collected and washed free of acetic acidformed in pyrolysis of the carbinol ester and the product isrecrystallized as usual.

EXAMPLE 1.6-METI-IOXY-2-NAPHTHYL METH- YLCARBINOL ACETATE Reduction of6-methoxy-Z-acetonaphthone (J. Chem. Soc., 1394 (1939)) Was carried outunder standard hydrogenation conditions. In a 300-cc. void stainlesssteel bomb there was placed 30 g. (0.15 mole) of6-methoxy-2-acetonaphthone, 175 cc. of methanol and 2 g. of a copperchromite catalyst. The bomb was pressurized with hydrogen such that at125 the pressure was 3050 p. s. i. At that temperature hydrogenationoccurred during one-half hour, after which time the pressure was 2650 p.s. i. The calculated cold drop was 300 pounds. Found 300 pounds. Thecatalyst was filtered and the reaction mixture evaporated to 75 cc. Uponaddition of excess hexane, 23 g. of a white solid precipitated (77%yield) which melted at 104-105". After recrystallization from benzene itmelted at 113.5-114.5.

Calculated for C13H14O2: C, 77.5; H, 7.1.

The white solid was treated with cc. of acetic anhydride and 1 cc. ofpyridine overnight on the steam cone. Distillation yielded 22 g. (79.5%)of a white solid, 6- methoxynaphthylmethylcarbinol acetate, boiling at138- 148/0 .3 mm. which after recrystallization'from hexane melted at60-61 C, 77.3; H, 7.0. Found:

Calculated for Ciel-11503: C, 73.8; H, 6.6. Found: C, 73.8; H, 6.7.

6-Meth0xy-2vinylnaphthalene A mixture of 22 g. (0.089 mole) of the6-methoxynaphthyl methylcarbinol acetate and 50 cc. of thiophenefreebenzene was passed dropwise at the rate of one drop per second through a25-min. O. D. Pyrex tube packed for a distance of 30 inches with glassbeads and heated to 500-510 C. by means of an electrically controlledfurnace. The reaction products were caught in a Dry Ice trap, melted andwashed free from acetic acid with water. The benzene was removed at thewater pump and the residue recrystallized from benzene-hexane to yield 6g. (36.5%) of product which melted at 9l92 C.

Calculated for CisHmO: C, 84.74; H, 6.57. Found: C, 84.2; H, 5.8.

In a slightly difierent procedure, the6-methoxy-2-naphtholmethylcarbinol acetate was passed through thepyrolytic tube packed with Pyrex Raschig rings at the same rate, thetemperature being from 495505 C. From 50 grams of starting material, 21grams of washed and hexane-recrystallized 6-methoxy-2-vinylnaphthalenewas obtained M. F. 93-94" and an additional 4 grams M. P. 91-92 from thehexane mother liquors.

EXAMPLE 2.-HOMOPOLYMERIZATION OF 6- METHOXY-Z-VINYLNAPHTHALENE Asolution of 1 g. of 6-methoxy-2-vinylnaphthalene and 0.01 g. of benzoylperoxide in 5 ml. of dioxane was heated 20 hours at 100. The polymer wasprecipitated by pouring the reaction mixture into excess ethanol.

Calculated for C12H1201n2 C, 84.8; H, 5.0. Found: C, 84.3; H, 6.3.

EXAMPLE 3.-COPOLYMERIZATION OF 6-METH- OXY 2 VTNYLNAPHTHALENE WITHMALEIC ANHYDRIDE EXAMPLE 4.FURTHER COPOLYMERS OF 6-METHOXY-Z-VINYLNAPHTHALENE A solution of 1 g. (0.054 mole) of6-methoxy-2-vinylnaphthalene, 0.054 mole of comonomer and 1% of totalmonomer weight of benzoyl peroxide in 5 cc. of dioxane was heated at 100for 24 hours and precipitation of the polymer carried out in solvents aslisted below:

Percent Solvent Pre- Comonomer cipitafion Ogggar- H N Styrene Methanol.63. 86. 5 6. 6 p-Methylstyrene. do 61. 0 86. 3 6.8 Methylacrylat-e -.do50. 0 79. 5 6. 2 Acrylamide Water 86.0 79. 0 6. 4 2. 0 AcrylonitriMethanoluu 69.0 85. 7 6. 3 2,5-Diacetoxystyrene do 68. 0 75. 0 6. 0

2,5-diacetoxystyrene is prepared by the method of Reynolds et a1. U. S.patent application Serial No. 282,456 filed April 15, 1952.

EXAMPLE 5.-l-METHOXY-2-NAPHTHYL METH- YLCARBINOL A mixture of 40 g. or0.2 mole of l-methoxy-Z-acetonaphthone, 4 g. of copper chromite catalyst(Harshaw Cu-X-649-57-P) and suflicient ethanol to make a final volume of150 cc. was hydrogenated at 115 c. until 0.2 mole hydrogen had beenabsorbed. The cooled reactor was opened, the contents filtered, and thealcohol evaporated at the water pump to give 36.8 g. of l-methoxy-2-naphthyl methyl carbinol, M. P. 89-91" C. The melting point of thesample or material recrystallized from hexane was 92-93 C.

1methoxy-2-vinylncrphthalene The carbinol prepared above was acetylatedas in Example 1 and the resulting l-methoxy-Z-naphthyl methylcarbinolacetate was pyrolyzed by the method of Example 1 to give1methoxy-Z-vinylnaphthalene. However, since the yield was very low thefollowing procedure can be used to advantage to obtain the compound bypyrolysis of l-metboxy-Z-naphthyl methylcarbinol:

A solution of 15 parts of l-methoxy-Z-naphthylmethylcarbinol in 200parts of thiophene-free benzene was passed during one-half hour througha glass tube packed with activated alumina and maintained at 350 bymeans of an electric furnace. By distillation there was obtained 1.6parts of 1methoxy-2-vinylnaphthalene, B. P. 83-84 C. (0.3 mm.).

EXAMPLE 6.-HOMOPOLYMERIZATION OF 1- METHOXY-2-VINYLNAPHTHALENE A 0.1 g.sample of l-methoxy-Z-vinylnaphthalene prepared above was heated with0.001 g. of benzoyl peroxide for 72 hours at C. to yield a clear hardpolymer.

Copolymers of 1-methoxy-2-vinylnaphthalene with other polymerizablecompounds such as those given above, are obtained by methods such asshown in Examples 3 and 4.

Other alkoxyvinylnaphthalenes such as 4-methoxy-1- vinylnaphthalene and6-methoxy-l-vinylnaphthalene can be prepared in the manner of the aboveexamples by pyrolysis of the corresponding alkoxynaphthylcarbinolacetate such as 4-methoxy-l-naphthylmethylcarbinol acetate and6-methoxy-l-naphthylmethylcarbinol acetate. The homopolymers andcopolymers of these alkoxyvinylnaphthalenes with polymerizable compoundssuch as those indicated above are prepared in a manner similar to thatset forth in the above examples.

What I claim is:

1. A compound selected from the group consisting of l-methoxy 2vinylnaphthalene and 6-methoxy-2-vinylnaphthalene.

2. lmethoxy-2vinylnaphthalene.

3. 6-methoxy-2-viny1naphthalene.

4. A resinous polymer of a compound selected from the group consistingof 1methoxy-Z-vinylnaphthalene and fi-methoxy-2-vinylnaphthalene.

5. A resinous polymer of l-methoxy 2 vinylnaphthalene.

6. A resinous polymer of 6-methoxy 2 thalene.

7. A resinous copolymer obtained by polymerizing a mixture comprisingl-methoxy-2-vinylnaphthalene and a different compound containing apolymerizable CH=C group.

8. A resinous copolymer obtained by polymerizing a mixture comprising-methoxy2-vinylnaphthalene and a dilferent compound containing apolymerizable --CH=C group.

9. A resinous copolymer obtained by polymerizing a mixture comprising6-methoxy-Z-vinylnaphthalene and a compound of the group consisting ofmaleic anhydride, styrene, p-methylstyrene, methacrylate, acrylamide,acrylonitrile, and 2,5-diacetoxystyrene.

10. A method for preparing 1-methoxy-2-vinylnaphthalene which comprisespassing l-methoxy-Z-naphthylmethylcarbinol acetate through a zone heatedto a term perature of from about 250600 C.

- vinylnaph- 5 6 11. A method for preparing G-methoXy-Z-vinylnaph-Bachmann et al.: Journal American Chemical Society, thalene whichcomprises passing @methoxy-Z-naphthylvol. 70, 1948, pages 1462-1468.methylcarbinol acetate through a zone heated to a tem- Cohen: JournalChemical Society, London, 1937, pages perature of from about 250-600 C.1315-1317 and 1319.

5 Kolesnikov et al.: Chemical Abstracts, vol. 45, 1951, References Citedin the file of this patent page 7553, being an abstract of Zhur.Obschei. Kheim,

UNITED STATES PATENTS 21, Pages -4 1951- 2,310,762 Danmmer et a1; Feb.9, 1943 Weygand: Organic Preparations, Interscience, 1945, 2522501 Bmkset a1 Sept 1950 10 ililflfinis zgl' fii n land Related Pol mars Wile1952 2,647,883 Evans et a1. Aug. 4, 1953 pages 159461" y Y OTHERREFERENCES Van Allan: Journal Org. Chem., vol. 16, pages 999- 1001,1951.

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF 1-METHOXY - 2 -VINYLNAPHTHALENE AND 6-METHOXY-2-VINYLNAPHTHALENE.